Adduct of p-quinone and phosphoric acid



Oct. 4, 1966 Original Filed GRAHS OF CORROSION L. FULLHART, JR., ETAL3,277,120

ADDUCT OF P-QUINONE AND PHOSPHORIC ACID Aug. 4, 1961 2 Sheets-$heet l\VAPOR LEVEL LIQUID LEVEL EFFECT OF OUINONE P I INITIAL SOLUTIOOSFPHORIC ACID ADDITION NTAINED 0.2% DNT A CURVE B QUINONE ADDITION IPRODUCT. I

- PRODUCT.

I5 6O 75 90 I05 I20 I I50 I I HOURS ON TEST INVENTOR5 LAWRENCE FULLHART,JR DONALD A.SWALHEIM ATTORNEY Oct 1966 L. FULLHART, JR, ETAL 3, 7

ADDUGT OF P-QUINONE AND PHOSPHORIC ACID Original Filed Aug. 4, 1961 2Sheets-Sheet. 2

EFFECT OF p-QUIIIOPIE OII THE CORROSION F 3I6 ST/IIIIILESS STEEL COILSI.IO

INITIAL CHA GE 0.2%0 T-0.2% p- Ul E z 80 CURVE A- N0 ADDITIONS CURVE B0.025% p QUINONE/ DAY 3 70 CURVE C- 0.05% -OUINONE/ DAY 3 CURVE D 0.l%p-QUINONE/ DAY 0: .60

I 45 so I5 90 I05 I20 I I50 I mo I95 ZIO 225 240 255 210 285 300HOURSOIII TEST EFFECT OF IIQRII LOAD fiI A'IIouIII 0F Bf-OUIPIOIIECORROSION Ho TO PROTECT 5I6 STA NLESS STEEL FRO INITIAL CHARGE 0.2%ONT-0.2% p-QUINONE 90 PLUS 0.05% DAILY ADDITIONS OF I -QUINONE WORK LOADI z 80 CURVE A I SQ. FT GAL. DAY. CURVE a as so. FT./ GAL. DAY. 6 URVE sa 10 3 2. 82.2.1225; 32m 560 .50 o g .40 A 5 L .20 ::l I o 1 0 I05 I20l55750 l65 I I 2I0 225 240 255 270 285 300 5I5 330 345 560 3"5 390LAWRENCE FULLHART, J R.

DONALD A S ALH E I M ATTORNEY United States Patent Oilice 3,277,120Patented Oct. 4, 1966 1 Claim. (Cl. 260-396) This application is adivision of application Serial No.

a 129,351, filed August 4, 1196 1.

This invention relates to the stabilization of chlorohydrocarbons and,more particularly, it relates to the stabilization of halohydrocarbonsunder high-1y acid conditions.

Throughout the specification and claims, the term halohydrocarbon refersto halo-substituted hydrocarbon solvents containing one to three carbonatoms including, for example, trichlorethylene, perchlorethylene,methylene chloride, methyl chloroform, carbon tetrachloride and,particularly, trichlorethylene and perchlorethylene,trifiuorotrichloroethane, difluorotetrachloroethane,dibromotetrafiuoroethane, dichlorotetrafiuoroethane, andtrichlorofiuoromethane.

Chlorohydrocarbons are extensively used in metal cleaning and degreasingoperations. Many stabilizers have been used to stabilizehalohydrocarbons, particularly chlorohydrocarbons, against deteriorationduring metal cleaning and degreasing operations.

These stabilizers function to prevent ha'lohydrocarbon deterioration inthe presence of heat, light and/ or oxygen under alkaline or neutralconditions. More recently, attempts have been made to phosphatize metalsurfaces in a halohydrocarbon-phosphoric acid solution. Such solutionsare prepared with the use of a sol-ubilizin-g agent for thesolubilization of the phosphoric acid in the halohydrocarbon, forexample, trichlorethylene. As examples of sol-ubilizing agents may benamed amyl and butyl alco hols, alkyl phosphates and the like. Theresulting highly acid trichlorethylene is unstable even in the presenceof previously known stabilizing agents. Such phosphatizingtrichlorethylene solution is particularly unstable when used for thephosphatizing of metals. For example, when phosphatizing iron surfacesthe phosphoric acid forms ferrous phosphate and releases nascenthydrogen, also referred to as free radical hydrogen. The nascenthydrogen reacts with the halohydrocarbon, for example, trichlorethylene,to decompose the same, releasing HCl. This HCl is much moredeteriorating and corrosive to metal surfaces, particularly equipmentsurfaces, than is phosphoric acid.

Still more recently, certain hydrogen accepting agents have beensuggested for the stabilization of halohydrocarbons under highly acidand met-a1 phosphatizing conditions. Such hydrogen accepting agentscomprise nitroaromatic compounds as disclosed in our copendingapplication, Serial No. 72,590, filed November 30*, 1960, now abandoned,and nitrosoaromatic and azoaromatic compounds as disclosed in ourcopending application, Serial No. 8 2,159, filed January 12, 1961, nowUS. Patent 3,051,595. Although such hydrogen accepting agents stabilizea halohydorcarbon against the formation of large amounts of HCl byaccepting nascent hydrogen released as a result of the acidphosphatization of metals, these compounds could not accept such HCl asmay have been formed therein. Hydrogen chloride acceptors presently usedin a number of trichlorethylene compositions are not useful inphosphatizing processes by reason of the presence of considerableamounts of phosphoric acid. In fact, the acceptance of HCl in thepresence of much larger amounts of phosphoric acid presented a majorobstacle to the successful phosphatizing of metals with a phosphoricacidhalo-hydrocarbon solution.

It is an object of this invention to stabilize a halohydrocarbon in thepresence of phosphoric acid.

It is another object of the invention to substantially eliminate acorrosive acid condition in a phosphoric acidhalo-hydrocarbon solution.

It is a further object to eliminate HCl formed in a solution ofphosphoric acid in a halohydrocarbon under metal phosphatizingconditions.

It is a still further object of this invention to prevent substantialformation of HCl under metal phosphatizing conditions in a phosphoricacid-halohydrocarbon solution and to eliminate any HCl that may beformed therein.

The objects of this invention are accomplished by the addition of astabilizing amount of a quinone to a phosphoric acid-halohydrocarbonsolution. The quinones function both to accept nascent hydrogen as wellas HCl formed in halohydrocarbon solution. Therefore, quinones may beused alone in a halohydrocarbonphosphoric acid solution to preventcorrosion of equipment. The quinones appear to boom hydroquinones byreacting with the nascent hydrogen, and it forms halohydroquinones, forexample, a chlorohydroquinone, by reaction with HCl. The property of aquinone whereby it is capable of accepting relatively small quantitiesof HCl in the presence of much larger quantities of phosphoric acid isapparently of a highly unique nature. The preferential reaction ofquinones to combine with HCl in the presence of phosphoric acid makesthem outstanding compounds as stabilizers in acid solutions such astrichlorethylene phosphatizing solutions. Since chlorohydrocarbons areby far the most important halohydrocarbons at the present time,reference will hereinafter be made specifically to chloro hydrocarbons,it being understood, however, that the conditions described withreference to the chlorohydrocarbons also prevail in the case offluoroand bromohydrocarbons as above named.

Of course, it may be expected that the type of decomposition describedabove with its attendant corrosion problems will be particularly severewhere the system employing a chlorohydrocarbon solvent is of design anacidic medium. This has been found to be the case in actual practiceand, for this reason, quinones of the present invention have particularutility in an anhydrous phosphatizing system employed in metal finishingoperation as a desired means of applying phosphate coatings to metalsurfaces to improve paint adhesion and reduce corrosion. In theexecution of such a system, which is highly acidic, metallic surface,are contacted with a composition consisting of a chlorohydrocarbonsolvent as a primary component with a phosphatizing amount of phosphoricacid and an agent which solubilizes the phosphoric acid in thechlorohydrocarbon solvent. Broadly, a phosphatizing amount of commercialorthophosphoric acid may be considered to be an amount betweenapproximately 0.05 and 7.5% by weight based on the total Weight of thebath. Representative of agents which may be used to solubilizephosphoric acid in the bath are lower molecular weight aliphaticalcohols containing from 3 to 8 carbon atoms and alkyl acid phosphatecompounds. Of these, the lower molecular weight alcohols, particularlybutyl and amyl alcohol, are preferred and based on the above-statedrange of phosphoric acid, an amount of the alcohol in the range of firom1 to 10% by Weight based on the total weight of the bath is preferred.

It has been found that anhydrous phosphatizing baths of this type may beconveniently employed as part of an integrated unit which also includessolvent degreasing and/or painting operations separated from thephosphatizing bath by suitable partitions but under a common vapor zoneof the ohlorohydrocarbon solvent. Due to the volatility of the hydrogenchloride and corrosive chlorides formed through the decomposition of thechlorohydrocarbon solvent by virtue of the acid medium in thephosphatizing bath, corrosion in the metal container of such anintegrated unit is not confined to the immediate vicinity of thephosphatizing bath but rather extends across the entire unit,particularly at the condensate region of the unit. Obviously, in orderfor the operation of such an integrated system to be commerciallysuccessful, decomposition of the chlorohydrocarbo-n solvent, and thecorrosion problems this decomposition presents, must be prevented.

The amount of the quinone stabilizing agents required to provideeffective stabilization of ohlorohydrocarbons is quite small and willvary to some extent with the in:

dividual quinone compound. As noted elsewhere, the amount of stabilizernecessary will vary with the amount of work being processed and, to somedegree, on the extent of other stabilizers present. In general, anamount between .001 and 1% by weight based on the amount ofchlorohyd-rocarbon will be preferred, although some stabilization occurseven when lower concentrations are employed. There is no upper limit inconcentration, but amounts over by weight offer no particular advantageand are not justified economically.

Corrosion of equipment in metal phosphatizing operations with phosphoricacid-chlorohydrooarbon solutions has been almost entirely eliminated andexceptionally desirable results from an economic point of view have beenobtained by combining the above-mentioned quinones with nitro, nit-rosoor azoaromatic compounds. These nitrogen-containing aromatic compoundsfunction to accept hydrogen released as a result of the metalphosphatizing and the slight amount of HCl formed under such conditionsappears to be accepted by the quinones.

In combining the quinones with the aforesaid nitrogencontaining aromaticcompounds in the phosphoric acidohlorohydrocarbon solution, the quinonemay be present in an amount between 0.001% and 5% and the nitro,'nitroso or azoaromatic may be present in an amount between 0.01% and5%, based on the weight of the phosphoric acid-hydrocarbon solution.

The phosphatizing solution of chlorohydrocarbon of this invention may,if desired, contain certain other known stabilizers.

In the following description, reference will be made to the accompanyingillustrations, in which,

FIGURE 1 is a diagrammatic side elevational view of a glass kettleequipped to measure corrosion of a metal coil;

FIGURE 2 is a plotted diagram showing the effect of p-quinone on thecorrosion of No. 316 stainless steel coils;

FIGURE 3 is a plotted diagram showing the effect of work load on a givenamount of p-quinone to protect the surface of No. 316 stainless steelfrom corrosion;

FIGURE 4 is a plotted diagram showing the effect of the addition productof p-quinone and phosphoric acid on the corrosion of No. 316 stainlesssteel.

The following detailed examples are given to illustrate the principlesof this invention.

ZINC DUST TEST The following laboratory test, hereinafter referred to asthe Zinc Dust Test has been devised to simulate the stabilizing actionof various stabilizing agents in an anhydrous chlorohydrocarbonphosphatizing bath operating under actual phosphatizing conditions onmetal surfaces. This test will be referred to in the examples thatfollow.

The basic bath composition for this test consists of 94.5% by weighttrichlorethylene, 0.5% by weight commercial orthophosphoric acid and 5%by weight of amyl alcohol as an agent to solubilize said phosphoric acidin the trichlorethylene. The trichlorethylene [used in the test was aso-called technical grade containing 0.01% by weight of pentaphen (paratertiary amyl phenol) and 0.3% by weight of diisobutylene as anoxidation stat bilizing system.

The test is carried out by adding 0.1 g. of high purity zinc dust to 500ml. of the above bath maintained at the reflux temperature. After tenminutes, the bath is filtered for the removal of insolubles and ml.thereof mixed thoroughly with an equal volume of water in a separatoryfunnel. The water layer is then decanted from the liquid mixture andanalyzed for water-soluble chlo? rides. The measured result of the testis the amount of chlorides present in parts per million and isconsidered to vary proportionately with the degree of trichlorethylene(filecomposition and corrosivity potential resulting there- Thefollowing tabulated results show the amount of chlorides, in parts permillion, found by carrying out the zinc dust test containing givenamounts of quinone stabilizers of the invention in comparison with acontrol containing no stabilizers except the pentaphen and diisobutylene contained in the trichlorethylene.

LIZERS Q,UINONES Concen- Ex. Stabilizer tration, Chloride's, N0. ,Welghtp.p.m.

Percent 1 p-Oninnrw Q 05 13 2 0. l 3 2 0. 2 1 4 0. 05 5 5 0. 1 1 6 d0 0.4 1 7 1,5-dihydroxyanthraquinone 0. 2 1 81,2,5,8-tetrahydroxyanthraquinone. 0. 2 1 9 D l-tert-butyl-p-quinone 0.1 12 in do 0.2 10 11 -dn 0. 4 7 12 Tetrachloro -p-quin0ne 0. 5 20 13p-Quinone phosphate addition product" 0. 2 4 l-amino-2-bromo-4-p-t01ueneanthraqulnone- 0. 4 20 2,3-d1carbethoxy- -benzoquinone 0. 28 152,5-dihydroxy-p-benzoquinone 0. 5 2 Quinhydrone 0. 5 12,6-dichloro-p-quinone 0. 2 20 2,5-dichloro-3,fi-dimethox 0. 2 .40 ..d o0. 4 20 2,5-d1ch1or0-p-qumone 0, 2 3O 1,2-naphthoquinone 0. 3 42-methy1-1,4-naphthoquinone 0. 3 15 1,Z-naphthoquiuone-t-sulfonic acidsodium salt 0. 3 25 Z-chloroanthraquinone 0. 3 152-methy1-1-nitroanthraquinone 0. 3 1 1-hydroxyanthraquinoue 0. 3 15Trichlorethylene (control) 50+ In the table, Example No. 13 constitutesthe addition product isolated by the addition of p-quinone totrichlorethylene containing 0.5% by weight of phosphoric acid.

CORROSION TEST Eflect 0f quinones on the corrosion of stainless steelWhile the reduction of chloride ion concentration is a good indicationof the prevention of trichlorethylene breakdown, it is also desirable todemonstrate that under practical conditions the phosphatizing solutionsof this invention are substantially non-corrosive. For this purpose, ademonstration was set up according to the following procedure. A glasskettle was equipped as shown in FIGURE 1 of the drawings. The kettle 8has a capacity of 3 liters. It is equipped with glass cooling coils 9,an air vent 10, a stopper 11, and a stainless steel coil 12 projectingtherethrough into that area of vapor level of the trichlorethylenephosphatizing composition. Means, such as a heating mantle, are providedto maintain the kettle at the reflux temperature of the solution.

The vessel is charged with 1500 cc. of technical grade trichlorethylenecontaining .3% diisobutylene and 0.01% pentaphen as oxidativestabilizers and 5.0% n-amyl alcohol, 0.2% clinitrotoluene (DNT) and 0.5commercial 85% orthophosphoric acid.

The stainless steel coil 12 is composed of No. 316 stainless steel andis carefully weighed. Cooling water is run through the glass condensercoil 9 as well as condenser coil 12. When the solution is brought toreflux, the coil 12 functions in the same manner as a cooling coil in acommercial unit. The coil 12 is removed at intervals as indicated andweighed. The loss in weight is a measure of corrosion.

In order to make this test typical of actual practice, iron powder wasadded each day to simulate work load. As stated previously, thephosphoric acid reacts with the metal surface to form iron phosphatewith the liberation of hydrogen. Thus, phosphoric acid is consumed inrelation to the square feet of metal surface introduced into the bath.Calculations from commercial units have shown that 17 sq. ft. of workrequire about 2 cc. of phosphoric acid. In the laboratory it was foundthat l g. of iron powder (high purity) required about 2 cc. ofphosphoric acid. Thus, iron powder has been used in the laboratory tosimulate commercial runs. In the present study 1.5 g. of iron powder wasadded each day to correspond to a work load of 64 sq. ft. per gal. ofbath per day. This level of work load is commensurate with that found inthe industry.

In Table II, Example 29, below, it can be seen that the addition ofp-quinone greatly reduced corrosion; in fact, it appears possible toprevent corrosion entirely. These results are also shown plotted inFIGURE 2 of the drawings in which curve A shows corrosion withoutaddition of p-quinone to bath. Curves B, C and D, respectively, showcorrosion results by addition of .025, .05 and .1 percent p-quinone perday.

Example 29 TABLE II.-EFFECT OF P-QUINONE ON CORROSION RATE OF 316STAINLESS STEEL OVER 11 DAYS Percent P-Quinone Work Load. Corrosion,Grams Per Day Sq. Ft./Gal./Day

illustrated in the following example which was performed in the samemanner as Example 29.

Example 30 In this test the rate of p-quinone addition was held constantat 0.05% and the work load varied from 170 sq. ft./gal/day to 21.25 sq.ft/gaL/day. Thus, 0.05% pquinone will prevent corrosion at a work rateof 42.5 sq. ft./gal./day while at higher work loads, increasing amountsof p-quinone are needed.

TABLE III.EFFECT OF WORK LOAD ON STABILIZING REQUIREMENTS OF P-QUINONERate of p-Quinone Addition in Percent Day Work Load,

Corrosion, Grams Sq. Ft./Gal./Day

1 15-day test.

These results are shown plotted in FIGURE 3 of the drawings.

In an attempt to analyze the phosphatizing solution for p-quinone it wasfound that after the solution had refluxed for several minutes, noquinone was present when determined by gas chromatography. The test wasthen repeated and analyzed at intervals to determine the rate ofdisappearance of the quinone. A solution composed of 93.5%trichlorethylene, 5% amyl alcohol, 0.5% phosphoric acid and 1% p-quinonewas refluxed for three hours. The results are given in Table IV.

Example 31 TABLE IV.STABILITY OF P-QULNONE IN TRICHLOR- ETHYLENE, AMYLALCOHOL AND PHOSPHORIC ACID BY GAS CHROMATOGRAPHY Percent of startingTime, hours: p-quinone DUST TEST AFTER 2 HR. REFLUX in PHOSPHATIZ- INGSOLUTION Concentration, percent Chlorides, p.p.m.

The nature of the quinone compound present in the phosphatizing solutionwas investigated. It was found that if a non-phosphatizing solution wasprepared with the other materials present as in Example 31, but withoutthe phosphoric acid, on refluxing 2 hours, no change in the p-quinonecontent took place as measured by gas chromatography.

Example 33 8 Example 34 TABLE VII.- EFFECT OF P-QUINONE PHOSPHORIC ACIDTABLE VI-STABILITY F P-QUIINONE TRICHLOR- ADDITION PRODUCT ON THECORROSION OF 316 STAIN- ETHYLENE A ND AMYL ALCOHOL BY GAS CHRO- LESSSTEEL MATOGRAPHY Percent f Startmg Percent p-Quinone Work Load Sq.

Tune, hours: p-qumone Addition Product Ft./Gal./Day Corrosion, Grams 1Test period 8 days.

H Cl acceptance of quinone in presence of phosphoric acid Aphosphatizing solution was prepared containing 0.4% p-quinone, .5%phosphoric acid, 5% amyl alcohol, 0.01% pentaphen and 0.3% diisobutyleneand the remainder trichlorethylene. To this solution was added twoconcentrations of hydrochloric acid. These solutions were titratedbefore and after 1 hour reflux. The data in Table VIII shows bytitration, the pick-up of hydrochloric acid in the presence ofphosphoric acid. Similar data 0 OH OH H I in Table IX show plck-up ofHCl in presence of qulnone- H01 H H quinone phosphoric acid additionproduct. In the concentration used, the puinone, or its phosphoric acidaddition rodq c p 01 not, reacted essentially quantitatively with thehydro- H H chloric acid.

0 0 oil Example OH 01 TABLE VIII.HYDROCHLORIC ACID ACCEPTANCE OFP-QUINONE IN TYPICAL PHOSPHATIZING SOLUTION H H HCl 11- 11 O1 H 35 Titerbefore Titer after H 01 H- C1 H-- 0 Solution Reflux, co. Reflux, cc.

H Y 0.1 N NaOH 1.0 N NaOH Control 22. 2 22. 0 Control plus 0.2 cc. conc.hydro- 24.2 22.6 cmoric i ii h dr 27 s 21 5 By reacting phosphoricacidwith p-quin one in chloro- 3322,? i cone y form a compound containingquinone and phosphorlc acid was isolated as follows:

To a solution of 19 g. (0.176 mole) of p-qulnone in Example 36 250 ml.of chloroform was added 11 cc. (.176 mole) of 85% phosphoric acid. Thereaction mixture was refluxed for three hours during which time a darkprecipitate formed. The chloroform was distilled ofi and the pre- TABLEIX. HYD R0 CHLO RIC ACID ACCEPTANCE OF PHOSPHORIC ACID ADDITION PRODUCTOF P-QUINONE cipitate Washed with water. The material had an in- 0 Titerbefore Titer after distinct melting point of approximately 199 C. Sampleif f a 6 f g if ag The p-quinone phosphoric acid addition product asisolated'was subjected to elemental analysis. The results solutionofTrmech, amylalcohol,

listed below indicate the compound is probably made up mme hosphateaddition product, and

of 1 molecule of p-quinone, 1 molecule of hydroquinone gydrochlm acidand 1 molecule of phosphoric acid.

Carbon Hydrogen Phosphorus Analysis Caled. Found Calcd. Found Calcd.Found CnH1 OaP 45. 46. 60 4. 12 3. 77 9. 98 8. 96

In Example 36, the difference in titer is 21.1 cc. 7 0 against acalculated difference of 24 cc. indicating 88% acceptance of HCl.

'I he p-quinone phosphoric acid addition product was shown to have astabilizing elfect on the phosphatizing solution by reducing chlorideion formation in the zinc dust test. Furthermore, in the corrosion testusing 316 stainless steel coils as described above, graded amountswereshown to reduce corrosion significantly (Table VII below and FIGURE4 of the drawings), 7

Efiect of quinone on efiective life of phosphatizing solution 5 One ofthe major factors affecting the economical op- 9 eration of aphosphatizing unit is the length of time a single solution willeffectively phosphatize. By effective phosphatizing is meant theformation of a coating weighing at least about 160 to 170 mg. per sq.ft. of surface. The bath life during which it will effectivelyphosphatize is influenced by the amount of foreign material carried intothe bath, by the parts being processed, decomposition of the stabilizersand solvent, and by vessel corrosion products. Thus, bath life can beextended by reducing any of these conditions. It has been found inaccordance with this invention that the presence of a quinone in thephosphatizing bath dramatically increases the bath life for effectivephosphatizing. The presence of the quinone largely prevents the entranceof metal salts that will inhibit phosphatization into the solution, andhydrochloric acid formation is reduced to a minimum since there is nobreakdown of the chlorinated solvent. For example, a standardphosphatizing solution consisting of trichloroethylene, 0.01% pentaphen,0.3% disisobutylene, 0.2% dinitrotoluene, 5% amyl alcohol and 0.5%phosphoric acid will produce a phosphate coating of 200 mg./sq. ft.while processing 200-300 sq. ft. of iron sheeting per gallon ofsolution, thereafter coating weights drop below 100 mg./sq. ft., whichis not commercially acceptable. In a similar composition which wasmaintained with the addition of 0.1% p-quinone, a coating Weight of 200mg./sq. ft. was maintained while processing 1000- 1500 sq. ft. ofsimilar iron sheeting per gallon of solution.

The effect of quinones in stabilizing phosphatizing so lutions is notlimited to trichloroethylene as used in the above examples but areequally effective in stabilizing other halogentated solvents used inthis manner. This is illustrated in Table X below, where numerous otherhalohydrocarbon solvents were tested by the Zinc Dust Test. In allcases, the quinones of this invention exhibit a protective influence asshown below.

Ex. No.

Test Solution Ch lorides,

ppm.

Unstabilizcd trichlorothyleue Unstabilized tri 2% pquiuone.'lriclllorotriiluoroethane lrichlorotrifluoroethane Totrnchloroethylene'Ietrnehloroethylcne Carbon tetrachloride Carbon tetrachloride 5%p-quinone 'lrichloroethylene 01% pentapheu .3%

diisobutylene. Trichloroetllylene 01% pentaphen 3% diisobutyleno 2%p-quinone. Trichloroethylene 111% pentaphen 3% diisobutylcne .3%l,5-dihydroanthrnquinone. 'lrichlorcthylene 01% pentaphen 3% 8diisobutylene 0.3% l hydroxyanthraquillOllG. Triohlorethylene 01%pentaphou 3% 5 diisobutyleuc 0.3% 1,Q-nuphthoquinone. Trichlorethylene01% pentaphon 3% diisobutylene 3% 1,Z-tlihydroxyanthra- DOUG. Carbontetrachloride 3% LQ-naphthoqui- 1 none.

o: to Us L1 m an cbaowenwc cz Throughout the specification and claims,any reference to parts, proportions and percentages refers to parts,proportions and percentages by Weight unless otherwise specified.

Since is is obvious that many changes and modification can be made inthe above-described details without departing from the nature and spiritof the invention, it is to be understood that the invention is not to belimited to said details except as set forth in the appended claims.

We claim:

The addition product of p-quinone and phosphoric acid comprising aboutone molecule of p-quinone, one molecule of hydroquinone and one moleculeof phosphoric acid; and having a melting point of about 199 C.

No references cited.

LORRAINE A. WEINBERGER, Primary Examiner.

DANIEL D. HORWITZ, Examiner.

L. A. THAXTON, Assistant Examiner.

